Method of molding intergral skin polyurethane foams having mold release properties

ABSTRACT

A process is disclosed which eliminates the necessity of applying a mold release agent to the mold when producing integral skinned polyurethane foam moldings in closed molds. This is accomplished by incorporating in the foamable reaction mixture an additive, which imparts mold release properties, said additive containing at least 25 aliphatic carbon atoms and being the salt of an aliphatic carboxylic acid and either a primary amine or an amine which contains either amide or ester groups.

Waited States Patent [19.1

Baden et a1.

1 Apr. 10, 1973 [75] Inventors: Heinrich Boden, Opladen; Wulf Von Bonin,Helmut Kleimann, Harald Mergard, all of Leverkusen, Leverkusen, Germany[73] Assignee: Bayer Aktiengesellschaft, Leverkusen, Germany [22] Filed:Oct. 21, 1970 [21] Appl. No.2 82,793

[30] Foreign Application Priority Data Oct. 24, 1969 Germany ..P 19 53637.9

[52] US. Cl ..264/48, 260/25 AC, 260/25 AZ, 260/18 TN, 264/53, 264/54,264/338, 264/D1G. 14 [51 int. Cl.....B29d 27/04, G08g 22/36, C08g 22/44[58] Field of Search ..260/2.5 AZ, 2.5 AC; 264/D1G. 14, 48, 54, 53,338

[56] References Cited UNITED STATES PATENTS 3,586,649 6/1971 Cobbledick.260/18 TN X 2,921,915 1/1960 Brochhagen et a1 ..260/2.5 AC UX 2,932,6214/1960 Terry ..260/2.5 AC 3,437,608 4/1969 Pohl ..260/2.5 AC UX3,222,303 12/1965 Hampson ..260/2.5 AC

FOREIGN PATENTS OR APPLICATIONS 214,810 5/1958 Australia ..260/2.5 AC879,167 3/1958 Great Britain ..260/25 AC 967,443 8/ 1964 Great Britain.260/2 5 AC 852,138 10/1960 Great Britain ..260/2.5 AC

587,370 11/1959 Canada ..260/2.5 AZ

651,638 1 l/ 1962 Canada ..260/2.5 AC

794,051 4/1958 Great Britain ..260/2.5 AC

1,160,042 7/ 1969 Great Britain ..260/2.5 AZ

1,367,045 7/1962 France ..260/2.5 AC 732,648 4/1966 Canada "260/25 ACOTHER PUBLICATIONS Wirtz, Hans Integral Skin Urethane Foam Molding inJournal of Cellular Plastics, Sept/Oct, 1969, pp. 304-309.

Primary ExaminerPhilip E. Anderson Attorney-Edward J. Whitfield [57]ABSTRACT A process is disclosed which eliminates the necessity ofapplying a mold release agent to the mold when producing integralskinned polyurethane foam moldings in closed molds. This is accomplishedby incorporating in the foamable reaction mixture an additive, whichimparts mold release properties, said additive containing at least 25aliphatic carbon atoms and being the salt of an aliphatic carboxylicacid and either a primary amine or an amine which contains either amideor ester groups.

7 Claims, No Drawings METHOD OF MOLDING INTERGRAL SKIN POLYURETHANEFOAMS HAVING MOLD RELEASE PROPERTIES LII precludes the necessity ofapplying a release agent to s the mold.

Polyurethane foams having an impervious outer skin and a cellular core,of the kind obtained by the moldfoaming method described, for example inGerman Auslegeschrift 1,196,864 and in co-assigned U. S. Pat. No.7l2,lll filed Mar. ll, 1968 and now abandoned are eminently suitable forthe mass production of lightweight structures, such as, for example, infumiture making, motor vehicle manufacture and house building.

The polyurethane moldings are produced by introducing a foamablereaction mixture comprising a polyisocyanate, a compound containing atleast 2 hydrogen atoms reactive with isocyanates and additives, into aclosed heatable mold, in which the foam expands and solidifies underhigh compression. The plastics material fills the mold exactly andreproduces the inner surfaces thereof.

It is preferred to use molds made of a material of extremely highthermal capacity and equally high thermal conductivity, preferably ametal. It is also possible, however, to use molds made of othermaterials, such as, for example, plastics, glass or wood.

In order to prevent the foamed molding from adhering to the surface ofthe mold during mold-release, the mold is conventionally provided with arelease agent. Waxes, soaps and oils are commonly used as mold releaseagents. These mold release agents form a thin film between the surfaceof the mold and the foamed molding which does not adhere either to themold or to the molding, and thus enables the molding to be readilyremoved from the mold.

Unfortunately, this method possesses several disadvantages in so far asmass production is concerned. The release agent has to be applied atregular intervals and during this period, the mold cannot be used. Inaddition, any engraving in the surface of the mold, for example animitation wood grain, becomes covered .with residues of release agentover a period of time. These firmly adhering residues are expensive toremove from the frequently complex contoured molds. Moreover, thefinished moldings are covered with a thin film of release agent, towhich lacquer systems do not readily adhere. Accordingly, the moldingshave to be ground before lacquering, or treated with solvents, toguarantee adequate adhesion of the lacquers to the molding.

It is therefore an object of this invention to provide a method ofproducing foamed moldings free of the disadvantages of prior artmethods. It is another object of this invention to provide a method ofproducing foamed moldings which dispenses with the necessity of applyinga mold release agent to the mold. It is a further object of thisinvention to provide a foamable mixture which has outstanding moldrelease properties.

The foregoing objects and others which will become apparent from thefollowing description are accomplished in accordance with the invention,generally speaking, by adding to the foamable reaction mixture salts ofaliphatic carboxylic acids and primary amines or amines containing amideor ester groups containing a total of at least 25 aliphatic carbon atomsdistributed between the amine and the carboxylic acid.

Since these salts internally lubricate the plastics mixture, theysimultaneously impart to the foamable reaction mixture outstanding flowproperties in the mold coupled with reduced bubble formation in thesurface of the finished molding. In addition, these additives have anantistatic effect.

A measure of the release effect is the force per cm which is required toopen the molds during mold release. The mold release forces which haveto be applied with the plastics containing the additives according tothe invention are lower than those which have to be applied with similarplastics when a release agent has been applied to the mold.

It is pointed out that the process of foaming in closed molds yields afoam which has a much greater density than that obtained when foaming iscarried out in open molds, and whose characteristics feature is a firmnoncellular non-porous outer skin which is considerably thicker than thecell walls inside the foam. Accordingly, this outer skin, which is thecharacteristic of the polyurethane foam obtained according to theinvention, and which largely determines its surface properties, is not afoam, which is particularly noticeable in the case of standard wallthicknesses of up to several millimeters. Accordingly, a foam of thiskind cannot be directly compared with the hitherto conventional foams,produced in open molds, which normally do not have a coherent outer skinor whose outer skin is comparable in its wall thickness with the cellwall thicknesses inside the foam. To this extent, it is not possible toderive any measures in regard to the mold release properties ofpolyurethane foams obtained by the process described above, from theformulations for conventional foams foamed in open molds because it isactually in the vicinity of the mold walls that the material does nothave the character of the foam.

Although in conventional foam recipes, fatty acids, sulphonic acids,tertiary fatty amines or other surfactants, have hitherto been used asactivators or as lubricants or extenders for delaying or promoting foamformation and as emulsifiers, there have not yet been any reportsrelating to the mold release properties of these materials in a foamcharacterized by a relatively thick homogeneous top layer of a non-foammaterial, nor are they seen to have any effect when the foams accordingto the invention are produced, or alternatively, any effect that theymay have is offset by other disadvantages.

Thus, the presence of sulphonic acid in the covering layer of thesefoams leads to reduced weather resistance, while foam formation can beadversely affected, i.e., delayed. Because they obviously cannot beincorporated in the polyurethane structure, tertiary amines tend toexude, and thus adversely affect the lacquering properties of thecovering layers. Products with pronounced surfactant properties are alsounsuitable, because they promote degradation of the surface throughhydrolytic influences.

According to the invention, these disadvantages are obviated byselecting a special combination of the additives used as release agents,by employing salts of aliphatic carboxylic acids with primary amines orwith amines containing amide groups or ester groups. To obtain asatisfactory release effect these salts must contain a total of at least25 aliphatic carbon atoms distributed between amine and acid.

This means that the amine can be a relatively shortchain amine when thecarboxylic acid has a long chain; or the carboxylic acid can have arelatively short chain when the amine has a long chain. It is preferred,however, that both the amine, whether a primary amine or an aminecontaining amide or ester groups, and the carboxylic acid should containmore than 12 aliphatic carbon atoms.

To explain the fact that it is only by using the amines referred toabove, that useful results are obtained without any adverse effects on,for example, the lacquering properties of the surface, it can be assumedthat primary amines react with excess isocyanates to form ureas which,like the amines containing amide groups or ester groups (which do nothave to have a primary character), are retained in the foam throughproton bridges or even through secondary reactions, and as a result donot exude. Although it is also possible in principle to use secondaryamines free from amide or ester groups, this does not provide such goodproperties in regard to mold release and affinity for lacquers.

Accordingly, the present invention relates to a process for theproduction of foams which comprises foaming a reaction mixture of apolyisocyanate, a compound containing reactive hydrogen atoms, water oran organic expanding agent and an additive in a closed mold, wherein theadditive is a salt, containing at least 25 aliphatic carbon atoms, of analiphatic carboxylic acid and a primary amine or an amine containingamide or ester groups.

In a preferred embodiment, the additive is a salt of a fatty acidcontaining at least 12 aliphatic carbon atoms.

In a particularly preferred embodiment, the additive is a salt of afatty acid containing at least 12 aliphatic carbon atoms, and a primaryamine containing at least 12 aliphatic carbon atoms or an aminecontaining amide or ester groups and having at least 12 aliphatic carbonatoms.

It is surprising that such salts are effective, since they containgroups which are able to react with isocyanates as a result of which:they should be deprived of any effect. In addition, there is nodeterioration in the quality of the foam although the additives, whenthey are monofunctional, should have resulted in chain breakages. Inaddition, the affinity for lacquers of the moldings produced with theadditives according to the invention is surprisingly not reduced. Theadditives used according to the invention are employed in quantities offrom about 0.1 percent to about 15 percent by weight, and preferably inquantities of from about 0.5 percent to about 2 percent by weight, basedon the total weight of foamable reaction mixture.

Polyisocyanates, and compounds contaiming at least two hydrogen atomsreactive with isocyanates, and additives of the kind described in largenumbers in Vieweg-Hochtlen, Kunststoffhandbuch Band VII Polyurethane areused in known manner for the preparation of the foamable reactionmixture.

According to the invention, it is possible to use polyisocyanates of anykind, preferably diisocyanates, such as, for example, tetramethylenediisocyanate, hextaining carbodiimide groups, uretdione groups, uretoneimine groups, biuret groups or isocyanurate groups. Mixtures of theaforementioned isocyanates may also be used. It is also possible to usereaction products of polyhydric alcohols with polyisocyanates, and alsopolyisocyanates of the kind used, for example, in accordance with GermanPatent Specifications Nos. 1,022,789 and 1,027,394.

In the present context, compounds containing at least two hydrogen atomsreactive with isocyanates preferably include polyhydroxyl compounds orpolyamines. These compounds preferably have molecular weights of fromabout 500 to about 10,000 and most preferably from about 800 to about5,000.

Suitable active hydrogen-containing compounds include, for example,linear or branched polyesters or polyester amides which are obtained byknown methods from monoor polyfunctional alcohols and carboxylic acidsor hydroxy carboxylic acids, optionally in the presence of aminoalcohols, diamines, hydroxyamines or amino carboxylic acids, and whichmay also contain hetero atoms, double bonds and triple bonds andmodifying radicals of unsaturated or saturated fatty acids or fattyalcohols. Other suitable compounds include linear polyalkylene glycolethers of varying molecular weights obtained by polymerizing alkyleneoxides, diethylene oxide, propylene oxide, styrene oxide,epichlorohydrin or tetrahydrofuran, and preferably those with a hydroxylgroup content of from about 0.5 percent to about 18 percent. It is alsopossible to use copolymers. In this way, the properties of the endproducts are often remarkably modified. Linear or branched additionproducts obtained by addition of the aforementioned alkylene oxideswith, for example, polyfunctional alcohols, amino alcohols or amines,are also suitable. The following are examples of polyfunctional startingcomponents for the addition of the alkylene oxides: water, ethyleneglycol, 1,2-propylene glycol, trimethylol propane, 1,2,4-butane triol,glycerol, pentaerythritol sorbitol and oligosaccharides and theiraqueous solutions, polysaccharides, castor oil, ethanolamine,diethanolamine, triethanolamine,

aniline, arylene diamines, alkylene diamines of the.

ethylene diamine, tetra of hexaethylene diamine type, and ammonia. It isof course also possible to use mixtures of linear and/or branchedpolyalkylene glycol ethers of different types. These polyalkylene glycolethers may also be used in admixture with other hydroxyl compounds oramines, for example, in admixture with 1,4-butylene glycol, trimethylolpropane, glycerol, 2,3-butylene glycol, pentaerythritol, tartaric acidesters, castor oil, or tall oil. Foaming of the polyalkylene glycolethers may also be carried out in mixtures with polyesters. For example,it is possible to use OH- group-containing polycarbonates, polyacetals,polyamides, polyactones, or polyactams; Cl or Ol-l-groupcontainingpolytetrahydrofurans or polybutadiones. OH- and/or Sl-Igroup-containingpolythioethers, phenols reacted with alkylene oxide, formaldehyderesins, hydrogenation products of ethylene-olefin-carbon monoxidecopolymers and epoxy resins; aminogroup-containing compounds, such asamino polyethers, polyesters or polyurethanes, and compounds containingcarboxyl groups and/or cyclic anhydride groups, which in addition maycontain ether, ester, amide, urea, urethane or thioether groups, arefurther examples of suitable compounds which react with isocyanates.

According to the invention, salts of aliphatic carboxylic acids andprimary amines or primary, secondary or tertiary amines containing amideor ester groups, the salt containing a total of at least aliphaticcarbon atoms, are used as additives. Although it is preferred to use astoichiometric mixture of acid and amine, deviations from thestoichiometric ratio of carboxyl groups to amino groups are alsoacceptable, although the excess of carboxyl or amino groups present, ifany, should not exceed 50 mol percent.

Preferred additives include those which are liquid at room temperatureand/or those which can be dissolved in one or more components of thefoaming mixture.

Monocarboxylic acids or polycarboxylic acids, which may be saturated orunsaturated and optionally even substituted, may be used as thecarboxylic acids, although it is preferred to use long-chain aliphaticmonocarboxylic acids with more than 12 carbon atoms, which may be linearor branched, of which the following are some examples: stearic acid,commercial coconut fatty acid mixtures, tallow or train-oil fatty acids,commercial paraffin fatty acids which generally are also in the form ofmixtures, undecylenic acid, oleic acid, linoleic acid, tall oil fattyacids, ricinoleic acid and the like. Oleic acid or tall oil fatty acidsare preferred.

The primary amines used for salt formation may be linear, branched,cyclic and may be monoamines, diamines or polyamines containing 2 ormore carbon atoms. It is preferred to use aliphatic monoamines with morethan 12 carbon atoms, such as, for example, the following: stearylamine,oleylamine, amines of ketones of commercial mixtures of long-chain fattyacids, for example a 9-amino-heptadecane mixture, tallow amines and thelike. So-called resin amines which can be obtained from resin acids, orabietylamine may also be used. The salts of 1 mol of oleic acid and 1mol of oleyl amine, 0.5 mol of ethylene diamine or 1 mol of 9-aminoheptadecane are particularly preferred.

Some amine compounds suitable for use according to the process of theinvention are for example, monoamines such as aminoethane, aminopropane,aminobutane, aminooctane, aminodecane, aminododecane, aminotetradecane,aminohexadecane, aminooctadecane, aminooctadecene, aniline,aminocyclohexane, p-nitroaniline, p-chloroaniline, p-ethoxyaniline,o-ethylaniline, m-aminobenzalacetophenone, 3 ,4-dichloroaniline,a-naphthylamine, N- ethylaminopropane, N-methylaminobutane, N-propylaminohexane, N-methylaniline, N-ethylaniline, di-N-butylamine,di-N-propylamine and the like; di-

and polyamines such as ethylenediamine, propylenediamine,butylenediamine, pentamethylenediamine, p-phenylenediamine,m-phenylenediamine, 2,4-diaminotolylene, 2,5- diaminotoluene,3,5-diaminotoluene, 2,6diaminotoluene, l-methyl-3 ,5-diethyl-2 ,6-diaminobenzene, l--methyl-3,5-diethyl-2,4- diaminobenzene,1,3,5-triethyl-2,6-diaminobenzene,

3 ,3-dimethyl-4,4'-diaminodiphenyl, 3 ,3 '-dimethoxy-4,4'-diaminodiphenyl, 3,3'-diethoxy-4,4'- diaminodiphenyl,4,4'-diaminodiphenylmethane, 4,4- d iaminodiphenyl dimethylmethane, l,5- diaminonaphthylene, 3 ,3 -dichloro-4 ,4 diaminodiphenylmethane,4,4-diaminodiphenylsulfone, 4,4'-methylene-bis( 2-chloroaniline) and thelike.

The amines containing amide or ester groups, may be primary, secondaryor preferably tertiary. They can be readily obtained for example byreacting diamines such as ethylene diamine, propylene diamine, N-dimethylamino-propylamine or even polyamines with fatty acids underamide-forming conditions, in which case the quantity in which the fattyacid is used should be selected in such a way that the amide formedstill has at least one free primary, secondary or preferably tertiaryamino group. Although in principle any aliphatic carboxylic acid,whether monocarboxylic or polycarboxylic may be used as the fatty acid,it is preferred to use saturated or unsaturated monocarboxylic acidscontaining more than 12 carbon atoms, such as the types givenhereinabove.

The amide-group-containing amine of N- dimethylaminopropylamine andoleic acid is particularly suitable, since it is easy to obtain on alarge scale.

In principle, the same considerations apply to the amines containingester groups, which are preferably tertiary. These can also be obtainedin a known manner by reacting the addition products of alkylene oxideswith primary or secondary amines, for example of alkanolamine such astriethanolamine, N-dimethylethanolamine, or N-dioleyl-ethanolamine, withthe aforementioned fatty acids under esterification conditions. Theamine of 3 mols of oleic acid and 1 mol of triethanolamine and3-dimethylamino-l-propyl oleic acid are particularly preferred. Theadditives are best prepared by directly mixing the carboxylic acid withthe amine, optionally in the melt or in solution. In a modification, theadditives are prepared by mixing the components in one or more of theconstituents of the foaming mixture.

In addition to fillers, dyes and other such additives, it is alsopossible to use flame-retarding additives, which may contain groupsreactive with isocyanates, such as, for example, reaction products ofphosphoric acid or phosphorous acid or phosphonic acids and alkyleneoxides or alkylene glycols and the like. Reaction products of dialkylphosphites, formaldehyde and dialkanolamines, and also flame-retardingagents which do not contain any groups reactive with isocyanates, forexample tris-2-chlorethyl phosphate, tricresyl phosphate, andtris-dibromopropyl phosphate may also be employed.

Activators are employed in the usual way in the preparation of thefoams, examples of which include dimethyl benzylamine, N-methyl-N-(N,N-dimethylaminoethyl)-piperazine, triethylene diamine, permethylateddiethylene diamine, tetramethyl guanidine, tris-hydroxymethyl-hexahydrotriazin'e, and organo tin compounds, such as, forexample, dibutyl tin dilaurate or stannous octoate. Stabilizers may alsobe used, examples of which include polyethers, polysiloxanes,sulphonated ricionoleic or oleic acid derivatives and their sodiumsalts. Water and/or low-boiling solvents, such as, for example,trichloro-monofluoromethane, dichloro-fluoromethane and methylenechloride, are used as expanding agents in quantities of at most about2.2 mols, based on 100 parts by weight of the compound containing groupsreactive with isocyanates and preferably in quantities of from about0.02 to about 0.08 mol.

The products obtained by the process according to the invention may beused in the production of furniture, airframes, technical apparatus andcomponents.

The invention is further illustrated by the following examples in whichall parts and percentages are by weight unless otherwise specified.

EXAMPLES A. Preparation of 9-aminoheptadecane oleate as the salt used inaccordance with the invention.

About 30 parts (106 mols) of oleic acid are mixed with stirring andmoderate cooling with about 25.5 parts 100 mols) of 9-aminoheptadecane(C C 19 mixture). The temperature rises to about 40C. After about 1hour, the temperature has fallen to room temperature, and the product isready for use. Viscosity 1 25 77 cp.

EXAMPLE 1 a. About 100 parts of an activated and stabilized polyolmixture (OH number 450, viscosity 1; 25 2300 cP) are stirred with about8 parts of monofluorotrichloro-methane, mixed in a two-component mixer(having a metering attachment) with about 133 parts of a polyisocyanateobtained by phosgenating the condensation product of aniline andformaldehyde (31.5% NCO, 1 25 320 c?) and introduced into a metal moldheated to about 60C. The mold measures about 900 X about 200 X about 10mm. The mold is coupled to a closure unit which enables the mold-releaseand moldopening forces to be adjusted. The molding has the followingphysical properties determined in accordance with DIN specifications53423 and 53424.

Flexural strength: E modulus: Tensile strength: Dimensional sta bilityunder heat:

5 ,B 400 460 kp/cm E, 8000 9000 kp/cm 8 ,B 160 200 kp/cm WB 120C.

EXAMPLE 2 a. About 100 parts of an activated and stabilized polyolmixture (OI-I number 500, viscosity 1; 25 950 c?) are stirred with about8 parts of monofluorol5 bility under heat:

Flexural srength: 8 ,8 500 6S0 kp/cm E modulus: E, 10,000 12,000 kp/cmTensile strength: Dimensional sta '6 ,B 190 230 kp/cm WB 120C,

b. As in Example 2a except that about 3 parts of the release agentaccording to the invention prepared according to A) are added to thepolyol mixture. The physical properties remain unaffected (cf. Table 1).

EXAMPLE 3 a. About 100 parts of an activated and stabilized polyolmixture (OI-I number 550, viscosity 7 25 1200 cP) are stirred with about8 parts of monofluorotrichloro-methane, mixed in a two-component mixer(having a metering attachment) with about 140 parts of polyisocyanateprepared by phosgenating the condensation product of aniline andformaldehyde (31.5% of NCO 1; 25 320 c?) and introduced into a metalmold heated to about 60C. of the kind described in Example la.

The physical properties of the plastics molding are determined inaccordance with DIN Specifications 53423 and 53424:

Flexural strength: E Modulus: Tensile strength: Dimensional sta bilityunder heat:

8 ,,B 550 600 kp/cm E ll,00 13,000 lip/cm 6 ,B 220 280 kp/cm WB 85 85C.

b. As in Example 3a except that about 3 parts of the release agentaccording to the invention prepared according to A) are added to thepolyol mixture. The

physical properties remain unaffected (cf. Table 1).

Although the invention has been described in considerable detail in theforegoing it is to be understood that such detail is solely for purposesof illustration and that many variations may be made by those skilled inthe art without departing from the spirit and scope of the invention.

What is claimed is 1. In a process for the production of molded articlesof integral skin polyurethane foam by foaming a reaction mixture, in aclosed mold, said reaction mixture comprising an organic polyisocyanate,an organic compound containing at least two hydrogen atoms reactive withisocyanates, and a blowing agent, the improvement which comprises addingto the reaction mixture from about 0.1 percent to about 15 percent byweight, based on the total weight of reaction mixture, of a mold releaseagent containing at least 25 aliphatic carbon atoms selected from thegroup consisting of a salt of an aliphatic carboxylic acid with aprimary amine; a salt of an aliphatic carboxylic acid with an aminecontaining amide groups, said amine containing amide groups being thereaction product of an aliphatic carboxylic TABLE 1 Specific moldopening force Release agent Mold (kpJemfi) Lacquerrelease N umber ingproplneortime of mold First Last erlies Example porated External (mills)releases mold release Assessment 5 5 0.8 1.5 A troublesome layer isformed on the surface of the mold a 5 1 8. Molding destroyed 50 0.8 0.8N 0 signs of any troublesome layers bein formed on the surface of themold. 5 50 0.8 5 50 O. 8 5 50 (l. 8 5 50 1.0 5 50 0. 8 5 50 0. s 5 500.8 X (lo 5 4 l). 8 Troublesome layer formed on the surface of the mold.

l 1.0 (l0 5 l 81) Molding destroyed 5 50 l. 2 l. 2 No troublesome layersformed on the. surface of the mold... 5 5t) 1.! LI. 5 50 Ll) l.(l. ll0 53 ll 3. 0 A lroulllesmne layer is formed on the surlzu-e of the mold.ll] l 0.0. H. r 5 3. 5 7. l) 1;: fort-e. No layers formed on thesurfaeeoflhe. mold. 5 5!) U. s l. 1) No signs ofany troublesome layers beingformed on the surface -I X +=lacqucr adhesion without pro-treatmentgood; =lacquer adhesion without pro-treatment poor. Lacquer systemstested: Dl) lacquers, polyester lacquers with polyisocyanates, acrylicresin lacquers, acidcatalyzed lacquers.

Nora:

I=aluminium stearate; II=9-aminoheptadecane cleats; III=oleyl acid and adior polyamine such that the amide contains at least one free primary,secondary or tertiary amine oleate; IV =methyl-bis (3-oleic acidamidopropyD-amino oleate;

V=amino oleate (amine obtained from resinie acids); VI=tris-ethyloleateamino oleate; VlI=0leic acid-N,N-diethylamino ethylester oleate;

V III=0leic aeid-(N,N-methyl phenylamino)-ethylester-2-oleate; IX=

ogiyc) acid-3-dimethylamino propylamide-l-oleate; X=s0ap solution 4. Theprocess of claim 1 wherein the aliphatic carboxylic acid is oleic acid.

5. The process of claim 1 wherein the amine is 9- aminoheptadecane.

6. The process of claim 1 wherein the compound containing at least 25aliphatic carbon atoms is 9- amino-heptadecane oleate.

7. The process of claim 1 wherein the amide group containing amine isthe reaction product of N- dimethylamino propylamine and oleic acid.

2. The process of claim 1 wherein the aliphatic carboxylic acid containsat least 12 aliphatic carbon atoms.
 3. The process of claim 1 whereinthe primary amine or the amine which contains amide or ester groupscontains at least 12 aliphatic carbon atoms.
 4. The process of claim 1wherein the aliphatic carboxylic acid is oleic acid.
 5. The process ofclaim 1 wherein the amine is 9-aminoheptadecane.
 6. The process of claim1 wherein the compound containing at least 25 aliphatic carbon atoms is9-amino-heptadecane oleate.
 7. The process of claim 1 wherein the amidegroup containing amine is the reaction product of N-dimethylaminopropylamine and oleic acid.